Structure - sensitivity Relationship

The chemistry behind the detonation of organic compounds is exceedingly complex and poorly understood, because it involves a variety of intermolecular reactions different from those observed during thermolysis in solution or in the gas phase [92-94], The conditions required to induce detonation of organic explosives vary widely and no clear-cut structure-sensitivity relationship exists. Nevertheless, most known explosives contain characteristic functional groups, and small molecules containing several of these should be handled with great care. 

The various structure-sensitivity relationships mentioned above typically treat different classes of compounds separately. Nitramines, for example, are not expected to fit on the same correlations as nitroaromatics or nitroheterocycles. Even within a given class, however, a variety of decomposition mechanisms may be operative. Indeed, Kamlet and Adolph found it necessary to establish two oxidant balance correlations for nitroaromatics [16], one being only for molecules having a CH—containing substituent alpha to a nitro group, 3 ... 

Law, K. Y, Tarnawsky, J. I. W. and Popovic, Z. D. (1994). Azo pigments and their intermediates—a study of the structure-sensitivity relationship of photogenerating bisazo pigments in bilayer xerographic devices. J. Imag. Sci. Technol, 38, 118-24. [204]... 

Yoshimoto A, Tobe H, Johdo O, Ishikura T, Takeuchi T. Structure sensitivity relationship of anthiacycline antibiotics to C7-reduction by redox enzymes, J Antibiot 1991 44 287—295. 

In this chapter we will briefly survey some of the most commonly used measures of sensitivity, as well as some earlier correlations between sensitivity and molecular properties. This will provide a basis for further discussion of factors affecting sensitivities and the subsequent presentation of correlations developed in our laboratory. It is often the exceptions to structure-sensitivity relationships that offer the greatest promise in broadening our understanding of the reactivities of energetic compounds. Studies of several exceptional systems will be presented and discussed in the light of unique structural or reactive features which can account for their observed behavior. 

There has been considerable elaboration of the simple Girifalco and Good relationship, Eq. XII-22. As noted in Sections IV-2A and X-6B, the surface ftee energies that appear under the square root sign may be supposed to be expressible as a sum of dispersion, polar, and so on, components. This type of approach has been developed by Dann [70] and Kaelble [71] as well as by Schonhom and co-workers (see Ref. 72). Good (see Ref. 73) has preferred to introduce polar interactions into a detailed analysis of the meaning of in Eq. IV-7. While there is no doubt that polar interactions are important, these are orientation dependent and hence structure sensitive. 

Enslein K, Gombar VK, Blake BW, Maibach HI, Hostynek JJ, Sigman CC et al. A quantitative structure-activity relationships model for the dermal sensitization guinea pig maximization assay. Food Chem Toxicol 1997 35 1091-8. 

The Danish EPA has developed an advisory list for self-classification of dangerous substances including 20 624 substances. The substances have been identified by means of QSAR models (Quantitative Structure-Activity Relationship) as having acute oral toxicity, sensitization, mutagenicity, carcinogenicity, and/or danger to the aquatic environment. 

Mansouri A, Makris DP and Kefalas P. 2005. Determination of hydrogen peroxide scavenging activity of cinnamic and benzoic acids employing a highly sensitive peroxyoxalate chemiluminescence-based assay structure-activity relationships. J Pharm Biomed Anal 39(l-2) 22-26. 

As in the case of the diffusion properties, the viscous properties of the molten salts and slags, which play an important role in the movement of bulk phases, are also very structure-sensitive, and will be referred to in specific examples. For example, the viscosity of liquid silicates are in the range 1-100 poise. The viscosities of molten metals are very similar from one metal to another, but the numerical value is usually in the range 1-10 centipoise. This range should be compared with the familiar case of water at room temperature, which has a viscosity of one centipoise. An empirical relationship which has been proposed for the temperature dependence of the viscosity of liquids as an Arrhenius expression is... 

Spsted, H. et al., Ranking of hair dye substances according to predicted sensitization potency quantitative structure-activity relationships, Contact Dermatitis, 51, 241, 2004. 

Rodford, R., et al., Quantitative structure-activity relationships for predicting skin and respiratory sensitization, Environ. Toxicol Chem., 22, 1855, 2003. 

Ashby, J., et al., Structure-activity relationships in skin sensitization using the murine local lymph node assay. Toxicology, 103, 177, 1995. 

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